Method for preparing variable-light transmittance article

ABSTRACT

Variable-transmittance articles, such as an ophthalmic lens, are prepared by applying to or incorporating within the article a combination of two (or more) organic photochromic substances exhibiting different activated absorption maxima within the matrix in which the substances are incorporated. One organic photochromic substance has an absorption maximum within the range of between greater than 590 and about 700 nanometers. The other organic photochromic substance exhibits at least one absorption maximum and preferably two absorption maxima, within the range of between about 400 and less than 590 nanometers. The organic photochromic substances are used in a proportion to achieve a near neutral coloring of the article. The article may also be tinted with a light compatible tint (dye) to achieve a more neutral color when the photochromic substances are activated.

This is a division of application Ser. No. 07/147,430, filed Jan. 25,1988 now U.S. Pat. No. 4,968,454.

DESCRIPTION OF THE INVENTION

The present invention relates to variable-light transmittance articles,a method for producing such articles, and photochromic compositionsuseful for preparing such articles. More particularly, the presentinvention relates to such articles and compositions in which theproperty of variable-light transmittance is provided by a combination ofcertain organic photochromic substances.

Attempts to produce a material whose spectral transmittance isreversibly variable according to the amount of light and the wave lengthof light that passes therethrough have led, in the field of organicchemistry, to the development of organic photochromic substances. Atransparent organic host material containing an organic photochromicsubstance has its transmittance reduced upon irradiation withultraviolet rays, such as from sunlight, the light of a mercury lamp, orvisible rays of short wave lengths (hereinafter referred to simply as"light"), but resumes its original transmittance when the irradiation isdiscontinued or the article stored in the dark.

When incorporated into transparent plastic ophthalmic articles, e.g., alens, and activated with "light", many organic photochromic substancesexhibit a narrow absorption band in the visible spectrum, which leads toa color, e.g., blue, that is not normally aesthetically acceptable tolens-wearing consumers. Preferably, an organic transparent materialcontaining a photochromic substance will, when activated with "light",change to a more near neutral color, such as neutral gray or neutralbrown. In particular, a neutral gray with or without a very slightbluish tint is expected to be most pleasing to consumers.

It has now been discovered that combinations of certain organicphotochromic substances will produce, when activated at roomtemperature, a more desirable near neutral color. More particularly, ithas been discovered that the appropriate combination of an organicphotochromic substance having an activated absorption maximum in thevisible range of greater than 590 nanometers, and an organicphotochromic substance having at least one activated absorption maximumin the visible range of between about 400 nanometers and less than 590nanometers can produce in a suitable matrix (when activated) a nearneutral color, e.g., a gray color. A color even closer to neutral grayfor the host material may be achieved, for example, by applying a smallamount of compatible tint (dye) to the photochromic substance-containinghost material.

DETAILED DESCRIPTION OF THE INVENTION

The first group of organic photochromic substances used in the practiceof the present invention are those having an activated absorptionmaximum of greater than 590 nanometers within the visible range.Preferably, the activated absorption maximum of this first group oforganic photochromic substances is at least 600 nanometers. Generally,the activated absorption maximum is between about 600 and 650nanometers, e.g., about 620 nanometers. Such organic photochromicsubstances typically exhibit a blue, bluish-green, or bluish-purplecolor when exposed to ultraviolet light in an appropriate solvent ormatrix. Examples of organic photochromic substances that exhibit such anactivated absorption maximum are spiro(indolino) naphthoxazines,spiro(indolino) pyridobenzoxazines, spiro(benzindolino) naphthoxazinesand spiro(benzindolino) pyridobenzoxazines. Mixtures of suchspiro(indoline)-type substances may be used in the practice of thepresent invention.

Spiro(indolino) naphthoxazines are well known in the art. See, forexample, U.S. Pat. Nos. 3,562,172, 3,578,602, 4,215,010, 4,342,668 andU.K. patent application 2,171,404. Spiro(indolino) pyridobenzoxazinesare described in U.S. Pat. No. 4,637,698. Spiro(benzindolino)pyridobenzoxaines and spiro(benzindolino) naphthoxazines are the subjectof co-pending and co-assigned U.S. patent application Ser. No. 78,325,filed July 27, 1987 now abandoned. The disclosures of the aforesaidpatents and patent application respecting such spiro(indoline)-typesubstances are hereby incorporated by reference.

Organic photochromic substances that have at least one activatedabsorption maximum in the visible range of between about 400 and lessthan 590 nanometers include spiro(indolino) benzoxazines. Suchbenzoxazines are described in co-assigned, co-pending U.S. patentapplication Ser. No. 929,936, filed Nov. 12, 1986, the disclosure ofwhich is hereby incorporated by reference. Mixtures of organicphotochromic substances exhibiting at least one absorption maximum, andpreferably two absorption maxima, in the described range between 400 andless than 590 nanometers may be used. The activated absorption maxima ofthis second group of photochromic substances are preferably in the rangebetween about 400 and about 570 nanometers. Photochromic substances,other than the described spiro(indolino) benzoxazines, that exhibit theaforedescribed activated absorption maxima may also be used alone or incombination with spiro(indolino) benzoxazines in the practice of thepresent invention.

The organic photochromic substances of Group I, i.e., those exhibitingan activated absorption maximum between greater than 590 and about 700nanometers, are selected to complement the organic photochromicsubstances of Group II, i.e., those exhibiting an activated absorptionmaximum of between about 400 and less than 590 nanometers, and viceversa. Thus, the photochromic substances of Groups I and II are selectedso that their respective activated absorption maxima are not close toone another; but, are sufficiently spaced apart so that when the spectraof the substances are combined there is a complementary rather than anadditive effect. That complementary effect results in a smoothing out orleveling of the combined spectra to produce a more neutral color ratherthan an enhanced single absorption maximum. In other terms, onephotochromic substance is selected so that it absorbs (when activated)in a region of the spectrum where the other photochromic substance doesnot absorb strongly, and vice versa.

The organic photochromic substances of Group I and Group II are combinedin amounts and in a ratio such that the organic host material containingsame exhibits a substantially neutral color when activated with light,e.g., a near neutral gray or brown color. A near neutral gray colorexhibits a spectrum that has relatively equal absorption in the visiblerange between 400 and 700 nanometers, e.g., between 440 and 660nanometers. A near neutral brown color exhibits a spectrum in which theabsorption in the 400-550 nanometer range is moderately larger than inthe 550-700 nanometer range.

An alternative way of describing color is in terms of its chromaticitycoordinates, which describe the qualities of a color in addition to itsluminance factor, i.e., its chromaticity. In the CIE system, thechromaticity coordinates are obtained by taking the ratios of thetristimulus values to their sum, e.g., x=X/X+Y+Z and y=Y/X+Y+Z. Color asdescribed in the CIE system can be plotted on a chromaticity diagram,usually a plot of the chromaticity coordinates x and y. See pages 47-52of Principles of Color Technology, by F. W. Billmeyer, Jr. and MaxSaltzman, Second Edition, John Wiley and Sons, N.Y. (1981).

The relative amounts of the photochromic substances of Groups I and IIrequired to obtain the desired near neutral color will vary and dependupon the activated absorption maxima exhibited by the specific organicphotochromic substances utilized. Generally, the mole ratio of the GroupI photochromic substance to the Group II photochromic substance may varyfrom about 1:0.5 to about 1:15, e.g., between about 1:4 and about 1:12,more particularly between about 1:6 and about 1:10. As used in thespecification and claims, a near neutral color is one in which thechromaticity coordinate values of "x" and "y" for the color are withinthe following ranges (D65 illuminant) x=0.260 to 0.400, y=0.280 to 0.400following activation to 40 percent luminous transmission by exposure tosolar radiation (Air Mass 1 or 2).

The organic photochromic substances of Groups I and II may be applied toor incorporated into the host material by methods known in the art; andthey may be applied to or incorporated into the host materialseparately, e.g., sequentially (in any order) or as a mixture. Further,when the host material is a transparent article, such as a lens, whichhas opposite surfaces exposed, it is contemplated that the organicphotochromic substance(s) of one Group may be applied to one side of thetransparent article and the organic photochromic substance(s) of theother Group applied to the opposite side, that the photochromicsubstances of both Groups be applied to one side of the transparentarticle (separately or together as a mixture) or to both sides of thearticle (separately or as a mixture).

Adjuvant materials may also be incorporated into the host with thephotochromic substances prior to or subsequent to their application orincorporation into the host material. For example, ultraviolet lightabsorbers may be admixed with photochromic substances before theirapplication to the host material or such absorbers may be superposed,e.g., superimposed, as a layer between the photochromic substance andthe incident light. Further, stabilizers may be admixed with thephotochromic substances prior to their application to the host materialto improve the light fatigue resistance of the photochromic substances.Stabilizers such as hindered amine light stabilizers and singlet oxygenquenchers, such as a nickel ion complex with an organic ligand, arecontemplated. They may be used alone or in combination. Such stabilizersare described in European patent application 195,898.

Compatible (chemically and color-wise) tints, i.e., dyes, may be appliedto the host material to achieve a more aesthetic result, for medicalreasons, or for reasons of fashion. The particular dye selected willvary and depend on the aforesaid need and result to be achieved. In oneembodiment, the dye may be selected to complement the color resultingfrom the activated photochromic substances, e.g., to achieve a moreneutral color or absorb a particular wavelength of incident light. Inanother embodiment, the dye may be selected to provide a desired hue tothe host matrix when the photochromic substances are unactivated.Finally, appropriate protective coating(s) may be applied to the surfaceof the host material. These may be abrasion resistant coatings orcoatings that serve as oxygen barriers, e.g., a polyvinyl alcoholcoating. Such coatings are known in the art.

Photochromic substances or compositions containing same may be appliedto or incorporated into a host material by various methods. Such methodsinclude dissolving or dispersing the substance within the host material,e.g., imbibition of the photochromic substance into the host material byimmersion or thermal transfer; incorporation of the photochromicsubstance as a separate layer between adjacent layers of the hostmaterial; and applying the photochromic substance as a coating to thehost material. The term "imbibition" or "imbibe" is intended to mean andinclude permeation of the photochromic substance alone into the hostmaterial, solvent assisted transfer absorption of the photochromicsubstance into a porous polymer, vapor phase transfer, and other suchtransfer mechanisms. For example:

(a) The photochromic substances or compositions containing same may bemixed with a polymerizable composition that, upon curing, produces apolymeric host material and the polymerizable composition cast as afilm, sheet or lens, injection molded or otherwise formed into a sheetor lens, or polymerized by emulsion or suspension polymerization to forma photochromic particulate material that may be used as a pigment;

(b) The photochromic substance may be dissolved or dispersed in water,alcohol or other solvents or solvent mixtures and then imbibed into thesolid host material by immersion of the solid host material for fromseveral minutes to several hours, e.g., 2-3 minutes to 2-4 hours, in abath of such solution or dispersion. The bath is conventionally at anelevated temperature, usually in the range of 50°-120° C.; however,higher temperatures may be used. Thereafter, the host material isremoved from the bath and dried;

(c) The photochromic substance and compositions containing same may alsobe applied to the surface of the host material by any convenient manner,such as spraying, brushing, spin-coating or dip-coating from a solutionor dispersion of the photochromic substance in the presence of apolymeric binder. Thereafter, the photochromic substance is imbibed intothe host material by heating it, e.g., in an oven, for from a minute toseveral hours at temperatures in the range of from 80°-180° C.;

(d) In a variation of the preceding imbibition procedure, thephotochromic substance or composition containing same may be depositedonto or absorbed by a temporary support, e.g., a sheet of kraft paper,aluminum foil, polymer film or fabric, which is then placed in nearproximity or in contact with the host material and heated, e.g., in anoven. This and the preceding procedure may be repeated one or more timesto imbibe the desired amount of photochromic substance into the hostmaterial;

(e) The photochromic substance may be dissolved or dispersed in atransparent polymeric material which may be applied to the surface ofthe host in the form of an adherent film by any suitable technique suchas spraying, brushing, spin-coating or dip-coating; and finally;

(f) The photochromic substance may be incorporated in or applied to atransparent polymeric material by any of the above-mentioned methods,which can then be placed within the host material as a discrete layerintermediate to adjacent layers of the host material(s).

In addition, imbibition of photochromic substances into a host materialmay be accomplished by the method described in U.K. Patent Application2,174,711, which is hereby incorporated in toto by reference. In thatmethod a substantially mottle-free, substantially homogeneous film ofpolymeric resin having the photochromic substance dissolved therein isapplied to the surface of the host material. The film-bearing hostmaterial is heated to temperatures near to but below the meltingtemperature of the photochromic substance for a time sufficient toincorporate a photochromic amount of the photochromic substance into thesurface of the host. The photochromic-lean film is then removed from thehost surface with a suitable solvent.

Imbibition of photochromic substances into a host material, e.g., anophthalmic lens, to produce a near neutral gray or brown color, asdescribed herein, may suitably be carried out by dissolving thephotochromic substances of Groups I and II that are to be used (in theirappropriate mole ratio) in a suitable solvent, e.g., toluene, andabsorbing the resulting solution into a temporary substrate, such asfilter paper or other substrates described in subparagraph (d) above.The concentration of the photochromic substances in the solvent may varyand will depend on the solubility of the substances in the solvent used.Suitably the photochromic substances will be present in the solvent at aconcentration of from about 5 to 15, e.g., 10, weight percent. Thetemporary substrate may be a flexible material that can take the shapeof the surface of the host material on which it is placed if suchsurface is irregular or not flat such as the curved surface of a lens.

The temporary substrate containing the solution of photochromicsubstances is dried to remove the solvent and the substrate placed incontact with the surface of the host material. Optionally, a metal caphaving the shape of the host material surface is placed on top of thetemporary substrate to insure uniform contact of the interface of thesubstrate and host surface. For example, when the host is a lens, thecap and temporary substrate should be shaped to conform to the shape ofthe lens, e.g., the convex or concave surface of the lens. This sandwichcomprising the metal cap-temporary substrate-host material is thenheated for a time sufficient to imbibe a photochromic amount of thephotochromic substances into the subsurface of the host material.Heating times may range from about 15 minutes to 120 minutes, usuallyfrom 45 to 90 minutes at transfer temperatures, which may range from145° C. to 155° C.

The aforesaid process may be repeated one or more times, e.g., at leasttwice, to imbibe the desired amount of the photochromic substances intothe surface of the host material, e.g., into a layer of the surface upto about 50 microns thick. In the case of semi-finished lenses, theimbibition process is performed on the front (convex) surface of thelens to allow finishing (grinding) of the back (concave) surface.Further, as described and claimed in a co-assigned application toanother, the edges of the lens may be ground to remove imperfectionsbefore thermally transferring the photochromic substances. If desired,the host material may then be tinted with a color compatible dye e.g., abrown, yellow-brown or gray dye. Typically, tinting is accomplished byimmersion of the host material in a heated aqueous dispersion of theselected dye. The degree of tint is controlled by the temperature of thedye bath and the length of time the host material is allowed to remainin the bath. Generally, the dye bath is at temperatures of less than100° C., e.g., from 70° C. to 90° C., such as 80° C., and the hostmaterial remains in the bath for less than five (5) minutes, e.g.,between about 0.5 and 3 minutes, e.g., about 2 minutes. The degree oftint is such that the resulting article exhibits from about 70 to 85percent, e.g., 80-82 percent, light transmission.

In the case of an ophthalmic lens imbibed with a combination ofspiro(indolino) pyrido benzoxazine and spiro(indolino) benzoxazinephotochromic substances, the lens may have a residual slightly yellowtinge after the imbibition process. A compatible dye, for example, amagenta dye, may be used to tint the lens to obtain a slightly brownishhue. The particular dye used to tint the photochromicsubstance-containing host material, as discussed, will depend on thecolor desired for the host material in its activated and/or unactivatedstate under conditions of use, e.g., temperature, and the amount andwave length of incident "light" on the lens.

Transparent (non-tinted) organic host materials, e.g., lenses preparedfrom polymerizates of diethylene glycol bis (allyl carbonate),containing the herein described combination of photochromic substancestypically exhibit a light transmission level of at least about 89percent in the unactivated state, when tinted, such materials mayexhibit an unactivated light transmission of between about 70 and 85percent, e.g., 80-82 percent. When irradiated with "light", such hostmaterials (whether or not tinted) may exhibit a light transmission levelranging from about 10 to about 60, e.g., 20 to 50, percent at ordinaryconditions (temperature and sunlight). Extremes of temperature andsunlight can affect the light transmission level.

Photochromic substances having an activated absorption maximum ofbetween greater than 590 and about 700 nanometers includespiro(indolino)-type compounds such as spiro(indolino) naphthoxazines,spiro(indolino) pyridobenzoxazines, spiro(benzindolino)pyridobenzoxazines and spiro(benzindolino) naphthoxazines. Suchspiro(indolino)type compounds may be represented by the followinggraphic formula: ##STR1## In the above graphic formula I, R₁ is selectedfrom the group consisting of C₁ -C₈ alkyl, e.g., methyl, ethyl, propyl,butyl, etc., phenyl, phen(C₁ -C₄)alkyl, e.g., benzyl, naphth(C₁-C₄)alkyl, e.g., 1-naphthylmethyl, allyl, acrylyl(C₂ -C₆)alkyl,methacrylyl(C₂ -C₆)alkyl, carboxy(C₂ -C₆)alkyl, e.g., β-carboxyethyl,γ-carboxypropyl and δ-carboxybutyl, cyano(C₂ -C₆)alkyl, e.g.,β-cyanoethyl, γ-cyanopropyl, β-cyanoisopropyl, and δ-cyanobutyl, C₁ -C₄acyloxy(C₂ -C₆)alkyl, i.e., [R_(c) C(O)OR_(d) --, wherein R_(c) is a C₁-C₄ alkyl and R_(d) is a C₂ -C₆ alkyl], e.g., acetoxyethyl,acetoxypropyl, propionyloxyethyl, acetoxybutyl, and propionyloxypropyl,hydroxy(C₂ -C₆)alkyl, e.g., hydroxyethyl, hydroxypropyl andhydroxybutyl, (C₂ H₄ O)_(m) CH₃, wherein m is a number of from 1 to 6,and mono- and di-substituted phenyl, said phenyl substituents beingselected from C₁ -C₄ alkyl and C.sub. 1 -C₅ alkoxy, e.g. methoxy,ethoxy, propoxy, butoxy and pentoxy. Preferably, R₁ is selected from thegroup consisting of C₁ -C₄ alkyl, phenyl, benzyl, 1-naphth(C₁ -C₂)alkyl,such as 1-naphthylmethyl, carboxy(C₂ -C₄)alkyl, cyano(C₂ -C₄)alkyl, C₁-C₄ acyloxy(C₂ -C₄)alkyl, e.g., C₁ -C₄ acyloxyethyl, hydroxy- (C₂-C₄)alkyl and (C₂ H₄ O)_(m) CH₃, wherein m is a number of from 1 to 3,e.g., 2.

R₂ and R₃ of formula I are each selected from the group consisting of C₁-C₅ alkyl, phenyl, mono- and di-substituted phenyl, benzyl, or R₂ and R₃may combine to form a cyclic ring selected from the group consisting ofan alicyclic ring containing from 6 to 8 carbon atoms (including thespiro carbon atom), norbornyl and adamantyl. The aforesaid phenylsubstituents may be selected from C₁ -C₄ alkyl and C₁ -C₅ alkoxyradicals. More particularly, R₂ and R₃ are each selected from C₁ -C₅alkyl, e.g., methyl, ethyl, propyl, butyl and pentyl, and phenyl. Whenone of R₂ or R₃ is a tertiary alkyl radical, such as tertiary butyl ortertiary amyl, the other is preferably an alkyl radical other than atertiary alkyl radical.

Y in graphic formula I may be carbon or nitrogen. The number and type ofnon-hydrogen substituent group represented by R₄ will vary dependingupon whether Y is carbon or nitrogen. Generally, when Y is carbon eachR₄ substituent may be selected from the group consisting of halogen,e.g., chloro, fluoro, or bromo, C₁ -C₅ alkyl, C₁ -C₅ alkoxy, e.g.,methoxy, ethoxy, propoxy, butoxy and pentoxy, nitro, cyano thiocyano, C₁-C₄ monohaloalkyl, e.g., C₁ -C₄ monochloralkyl, such as chloromethyl andchloroethyl, C₁ -C₂ polyhaloalkyl, as, for example, trihaloalkyl such astrichloroalkyl or trifluoroalkyl, e.g., trifluoromethyl and2,2,2-trifluoroethyl, and monoalkylamino or dialkylamino wherein thealkyl moiety of the alkylamino group contains between one to four carbonatoms, e.g., methylamino, ethylamino, propylamino, dimethylamino anddiethylamino.

The letter "e" in graphic formula I is an integer of from 0 to 2, e.g.,1, and denotes the number of non-hydrogen substituents. In particular,when "e" is 1 or 2 and Y is carbon, each R₄ substituent may be selectedfrom the group C₁ -C₂ alkyl, C₁ -C₂ alkoxy, chloro, fluoro, bromo,nitro, and trifluoromethyl. When "e" is 0 (zero), there are nonon-hydrogen substituents and all of the aromatic carbon atoms havetheir full complement of hydrogen atoms.

When Y is nitrogen, each R₄ non-hydrogen substituent may be selectedfrom C₁ -C₅ alkyl, e.g., C₁ -C₂ alkyl, C₁ -C₅ alkoxy, e.g., C₁ -C₂alkoxy, and halogen, e.g., chloro, fluoro or bromo. Typically, "e" is 0(zero) when Y is nitrogen and thus there are no non-hydrogensubstituents.

R₅ in graphic formula I may be selected from C₁ -C₅ alkyl, halogen, C₁-C₅ alkoxy, nitro, cyano, C₁ -C₄ monohaloalkyl, C₁ -C₄ polyhaloalkyl, C₁-C₈ alkoxycarbonyl, C₁ -C₄ acyloxy, i.e., R_(c) C(O)O--, wherein R_(c)is a C₁ -C₄ alkyl, e.g., methyl, phenylene and substituted phenylene,wherein such phenylene substituents may be selected from the groupconsisting of halogen, C₁ -C₅ alkyl, C₁ -C₅ alkoxy, cyano, C₁ -C₈alkoxycarbonyl, C₁ -C₂ polyhaloalkyl, C₁ -C₄ monohaloalkyl andmonoalkylamino or dialkylamino, wherein the alkyl moiety of thealkylamino group contains from 1 to 4 carbon atoms. The number ofsubstituents on the phenylene group may range from 0 to 2 and may be thesame or different. The letter "d" in graphic formula I may vary from 0to 4, e.g., 0 to 2, such as 1 or 2, and denotes the number ofnon-hydrogen substituents. When one R₅ substituent is phenylene orsubstituted phenylene, the letter "d" is 1 or 2. In that event, when "d"is 2, the second substituent is other than a phenylene or substitutedphenylene group. When "d" is 0 (zero), there are no non-hydrogensubstituents as described with respect to "e".

More particularly, spiro(indolino) pyridobenzoxazines that may be usedin the practice of the present invention may be represented by thefollowing graphic formula: ##STR2##

In graphic formula II, R₁, R₂ and R₃ are the same as defined withrespect to graphic formula I. R'₄ may be selected from C₁ -C₅ alkyl,e.g., C₁ -C₂ alkyl, C₁ -C₅ alkoxy, e.g., C₁ -C₂ alkoxy and halogen,e.g., chloro, fluoro or bromo. The letter "e" may vary from 0 to 1.Commonly "e" is 0, and thus, there are no non-hydrogen substituents.When "e" is 1, the R'₄ substituent may be located on any of theavailable carbon atoms of the pyridobenz moiety of the pyridobenzoxazineportion of the compound, i.e., at the 5', 6', 8', 9' or 10' positions,most usually at the 8', 9' or 10' positions. When "e" is 2, the R'₄substituent may be the same or different and, in either case, areselected from the above-described group and are located at two of theaforedescribed available carbon atoms.

R'₅ in graphic formula II may be selected from the group consisting ofC₁ -C₅ alkyl, e.g., methyl, ethyl, propyl, butyl and pentyl, halogen,e.g., chloro and fluoro, C₁ -C₅ alkoxy, e.g., methoxy, ethoxy, propoxy,butoxy and pentoxy, nitro, cyano, C₁ -C₄ monohaloalkyl, e.g.,chloromethyl, fluoromethyl, chloroethyl, chloropropyl, etc., C₁ -C₄polyhaloalkyl, e.g., trihaloalkyl, C₁ -C₈ alkoxycarbonyl, and C₁ -C₄acyloxy, i.e., R_(c) C(O)O--, wherein R_(c) is a C₁ -C₄ alkyl, e.g.,methyl. An example of an acyloxy group is acetoxy. While any halogen,i.e., chlorine, bromine, iodine and fluorine may be used in respect tothe aforesaid halogen or haloalkyl substituents, chlorine, fluorine andbromine, particularly chlorine and fluorine is preferred for the halogensubstituent and fluorine is preferred for the polyhaloalkyl substituent,e.g., trifluoromethyl, (CF₃). Preferably, R'₅ is selected from the groupconsisting of C₁ -C₂ alkyl, chlorine, fluorine, C₁ -C₂ trihaloalkyl,e.g., trihalomethyl such as trifluoromethyl and C.sub. 1 -C₅ alkoxy.

The letter "d" in graphic formula II is an integer from 0 to 4, e.g., 0to 2, such as 1 or 2. When "d" is 2 or more, the R'₅ substituent may bethe same or different and in either case, are selected from theaforedescribed group. The R'₅ substituent(s) may be located on any ofthe available carbon atoms of the indolino portion of the compound,i.e., at the 4, 5, 6 or 7 positions. When "d" is 2, the R'₅ substituentsmay be present at the 4 and 5, 5 and 6, 4 and 7 or 6 and 7 carbon atomsof the indolino moiety.

The spiro(indolino) pyridobenzoxazines may be synthesized by reaction ofthe corresponding nitroso-hydroxy quinoline with the corresponding freeindoline (Fischer's base) or indolium salt, e.g., the iodide salt,compound Such compounds and their synthesis are described in U.S. Pat.No. 4,637,698, which is incorporated herein by reference.

It is possible that the photochromic organic substances of graphicformula II (and III) can be a mixture of isomers due to the alternativedirectional mechanism by which intramolecular condensation occurs duringformation of the starting indole reactant (Fischer's base). Indolizationof 3-substituted phenylhydrazones can give rise to a 4-substitutedindole, a 6-substituted indole, or mixtures thereof. Thus, when "d" is1, the photochromic substance may be substituted at the 4 position onthe indoline ring, at the 6 position of that ring or comprise a mixtureof such isomers. When "d" is 2, the photochromic substance may besubstituted at any combination of the 4, 5, 6, or 7 carbon atoms of theindoline ring (as heretofore indicated) and may comprise an isomericmixture of such compounds, e.g., a mixture of compounds havingsubstituents at the 4 and 5, 4 and 6, 5 and 6, 4 and 7, 5 and 7, and 6and 7 positions of the indoline ring. Commonly, when "d" is 2 thesubstituents are located at the 4 and 5, or 5 and 6 positions. Alsocontemplated are materials containing mixtures of such isomers. e.g.,materials comprising 4 (and 6) and 5-substituted spiro(indolino)benzoxazines.

Examples of spiro(indolino) pyridobenzoxazines selected from thedescription of graphic formula II that may be employed in the process ofthe present invention as described in Table I. Such pyridobenzoxazinesare those in which R₁, R₂, R₃, and R'₅ are as indicated in Table I, theletter "e" is 0 (zero), and the letter "d" is 0, 1 or 2. A hyphen (-)indicates the absence of a non-hydrogen substituent.

                  TABLE I                                                         ______________________________________                                        Compound/                                                                              R.sub.1  R.sub.2 R.sub.3                                                                              R.sub.5 '                                                                            R.sub.5 '                             ______________________________________                                        1        CH.sub.3 CH.sub.3                                                                              CH.sub.3                                                                              --     --                                   2        CH.sub.3 CH.sub.3                                                                              CH.sub.3                                                                             4-CH.sub.3                                                                           5-CH.sub.3                            3        CH.sub.3 CH.sub.3                                                                              CH.sub.3                                                                             5-OCH.sub.3                                                                           --                                   4        CH.sub.3 CH.sub.3                                                                              CH.sub.3                                                                             5-C1   6-CH.sub.3                            5        CH.sub.3 CH.sub.3                                                                              C.sub.2 H.sub.5                                                                       --     --                                   6        CH.sub.3 CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      5-CH.sub.3                                                                           6-CH.sub.3                            7        CH.sub.3 C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                       --     --                                   8        n-C.sub.4 H.sub.9                                                                      CH.sub.3                                                                              C.sub.2 H.sub.5                                                                       --     --                                   9        CH.sub.3 CH.sub.3                                                                              phenyl  --     --                                   10       CH.sub.3 phenyl  phenyl  --     --                                   11       C.sub.2 H.sub.5                                                                        CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      4-CH.sub.3                                                                           5-CH.sub.3                            12       n-C.sub.4 H.sub.9                                                                      CH.sub.3                                                                              C.sub.2 H.sub.5                                                                      5-CH.sub.3                                                                           6-CH.sub.3                            13       CH.sub.3 CH.sub. 3                                                                             CH.sub.3                                                                             5-CH.sub.3                                                                           6-CH.sub.3                            14       n-C.sub.3 H.sub.7                                                                      CH.sub.3                                                                              CH.sub.3                                                                             5-OCH.sub.3                                                                           --                                   ______________________________________                                    

Compound 2 in Table I may be named 1,3,3,4,5-pentamethylspiro[indolino-2,3' [3H]pyrido [3,2-f] [1,4] benzoxazine]. Similarly,compound 6 in Table I may be named 1,3,5,6-tetramethyl-3-ethylspiro[indolino-2,3' [3H] pyrido [3,2-f] [1,4] benzoxazine]. Other compoundsin Table I can be similarly named taking into account the differentsubstituents. Moreover, compounds selected from the description ofgraphic formula II may be similarly named by substituting thesubstituents described with respect to R₁, R₂, R₃, R'₄ and R'₅ for thosefound in Table I. When the letter "e" is 1 or more, the R'₄substituent(s) are given a prime (') designation. Numbering of thepyrido benzoxazine portion of the molecule is counter clockwise startingwith the nitrogen atom of the oxazine ring as the 1' position.

Spiro(indolino)naphthoxazines that may be used in the practice of thepresent process may be represented by the following graphic formula:##STR3## wherein R₁, R₂ and R₃ are the same as that described withrespect to graphic formula I.

R"₄ in graphic formula III may be selected from the group consisting ofhalogen, e.g., chloro, fluoro or bromo, C₁ -C₅ alkyl, C₁ -C₅ alkoxy,e.g., methoxy, ethoxy, propoxy, butoxy and pentoxy, nitro, cyano,thiocyano, C₁ -C₄ monohaloalkyl, e.g., C₁ -C₄ monochloroalkyl, such aschloromethyl and chloroethyl, C₁ -C₂ polyhaloalkyl, as for example,trihaloalkyl, such as trichloroalkyl or trifluoroalkyl, e.g.,trifluoromethyl and 2,2,2-trifluoroethyl, and monoalkylamino ordialkylamino, wherein the alkyl moiety of the alkylamino group containsfrom 1 to 4 carbon atoms, e.g., methylamino, ethylamino, propylamino,dimethylamino and diethylamino. More particularly, the R"₄ substituentmay be selected from the group C₁ -C₂ alkyl, C₁ -C₂ alkoxy, chloro,fluoro, bromo, nitro and trifluoromethyl. The letter "e" in graphicformula III is a number from 0 to 2, e.g., 1 or 2, and denotes thenumber of non-hydrogen substituents. When "e" is 0, all of thesubstituents on the available carbon atoms of the naphtho moiety of themolecule represented by formula III are hydrogen.

As in the case with graphic formula II, when "e" is 1, the R"₄substituent may located on any of the available carbon atoms of thenaphtho moiety of the naphthoxazine portion of the molecule, i.e., atthe 5', 6', 7', 8', 9' or 10' positions. Preferably, the R"₄ substituentis present on the 7', 8' or 9' carbon atoms. When "e" is 2, the R"₄substituents may be same or different and in either case are selectedfrom the above-described group. When "e" is 2, the R"₄ substituents arecommonly located at the 7' and 9' or 8' and 10' positions. Numbering ofthe naphthoxazine portion of the molecule is done in the same manner asthat described with regard to the pyrido benzoxazine portion of themolecule of formula II.

Spiro(indolino) naphthoxazines and their synthesis are described in, forexample, U.S. Pat. Nos. 3,562,172, 3,578,602 and 4,215,010. Examples ofspiro(indolino) naphthoxazines selected from the description of graphicformula III that may be used in the practice of the present inventionare described in Table II. Such spiro(indolino) naphthoxazines are thosein which R₁, R₂, R₃, R"₄, and R"₅ are as indicated in Table II, theletter "d" is 0, 1 or 2 and the letter "e" is 1. As in Table I, a hyphen(-) indicates the absence of a non-hydrogen substituent. In Table II,all of the R"₄ substituents are at the 9'-position.

                                      TABLE II                                    __________________________________________________________________________                              R.sub.4 "                                           Compound/                                                                            R.sub.1                                                                            R.sub.2                                                                              R.sub.3                                                                              (9'-)                                                                             R.sub.5 "                                                                          R.sub.5 "                                  __________________________________________________________________________    1      CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                          --   --                                        2      CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                         5-CH.sub.3                                                                         6-CH.sub.3                                 3      CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                         5-OCH.sub.3                                                                         --                                        4      CH.sub.3                                                                           CH.sub.3                                                                             CH.sub.3                                                                             OCH.sub.3                                                                         5-Cl 6-CH.sub.3                                 5      CH.sub.3                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                          --   --                                        6      CH.sub.3                                                                           CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                         5-CH.sub.3                                                                         6-CH.sub.3                                 7      CH.sub.3                                                                           C.sub.2 H.sub.5                                                                      C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                          --   --                                        8      n-C.sub.4 H.sub.9                                                                  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                          --   --                                        9      CH.sub.3                                                                           CH.sub.3                                                                             phenyl OCH.sub.3                                                                          --   --                                        10     CH.sub.3                                                                           phenyl phenyl OCH.sub.3                                                                          --   --                                        11     CH.sub. 3                                                                          p-C.sub.6 H.sub.4 OCH.sub.3                                                          p-C.sub.6 H.sub.4 OCH.sub.3                                                          OCH.sub.3                                                                          --   --                                        12     C.sub.2 H.sub.5                                                                    CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                         5-CH.sub.3                                                                          --                                        13     n-C.sub.4 H.sub.9                                                                  CH.sub.3                                                                             C.sub.2 H.sub.5                                                                      OCH.sub.3                                                                         5-CH.sub.3                                                                          --                                        __________________________________________________________________________

Compound 2 in Table II may be named1,3,3,5,6-pentamethyl-9'-methoxyspiro [indolino-2,3' [3H]-naphth [2,1-b][1,4]-oxazine]. Similarly, compound 6 in Table II may be named1,3,5,6-tetramethyl-3-ethyl-9'-methoxyspiro [indolino-2,3' [3H]-naphth[2,1-b][1,4]-oxazine]. Other compounds in Table II can be similarlynamed taking into account the different substituents. Moreover,compounds selected from the description of graphic formula III may besimilarly named.

When the R₅ substituent in gaphic formula I is phenylene, i.e.,ortho-phenylene, or substituted phenylene, the spiro(indolino)-typecompounds depicted are spiro(benzindoline) pyridobenzoxazines andspiro(benzindolino) naphthoxazines. Such compounds may be represented bythe following graphic formula: ##STR4##

Ring B in graphic formula IV represents a substituted or unsubstitutedbenzene ring fused to the six membered ring of the indolino segment ofthe depicted molecule Ring B may be fused at the e, f, or g face of theindolino portion of the compound Preferably, ring B is fused at the e org face, as represented respectively by graphic formulae IVA and IVB:##STR5##

When ring B is fused at the e face, the compounds are numbered asdepicted in graphic formula IVA'. When ring B is fused at the g face,the compounds are numbered as depicted in graphic formula IVB'. ##STR6##As with respect to the description respecting graphic formula I, Y informula IV is carbon or nitrogen and R₁, and R₂ and R₃ are the same asdescribed with respect to graphic formula I.

When Y is carbon, the R₄ substituent(s) is graphic formula IV may beselected from the group consisting of halogen, e.g., chloro, fluoro orbromo, C₁ -C₅ alkyl, C₁ -C₅ alkoxy, e.g., methoxy, ethoxy, propoxy,butoxy and pentoxy, nitro, cyano, thiocyano, C₁ -C₄ monohaloalkyl, e.g.,C₁ -C₄ monochloroalkyl such as chloromethyl and chloroethyl, C₁ -C₂polyhaloalkyl, as for example trihaloalkyl such as trichloroalkyl ortrifluoroalkyl, e.g., trifluoromethyl and 2,2,2-trifluoroethyl, andmonoalkylamino or dialkylamino wherein the alkyl moiety of thealkylamino group contains from 1 to 4 carbon atoms, e.g, methylamino,ethylamino, propylamino, dimethylamino and diethylamino. The letter "e"in formula IV is an integer of from 0 to 2, e.g., 1 or 2 and denotes thenumber of non-hydrogen substituents. In particular, when e is 1 or 2,each R₄ substituent may be selected from the group C₁ -C₂ alkyl, C₁ -C₂alkoxy, chloro, fluoro, bromo, nitro, and trifluoromethyl.

When Y is carbon and "e" is 1, the R₄ substituent may be located on anyof the available carbon atoms of the naphtho moiety of the naphthoxazineportion of the compound, i.e., at the 5', 6', 7', 8', 9' or 10'positions. Preferably, the R₄ substituent is present on the 8' or 9'carbon atoms, more usually at the 9' carbon atom. When "e" is 2, the R₄substituents may be the same or different and, in either case, areselected from the above-described group. When "e" is 2, the R₄substituents are commonly located at the 7' and 9' or 8' and 10'positions.

When Y is nitrogen, the R₄ substituent(s) may be selected from C₁ -C₅alkyl, e.g., C₁ -C₂ alkyl, C₁ -C₅ alkoxy, e.g., C₁ -C₂ alkoxy, andhalogen, e.g , chloro, fluoro or bromo. Typically, e is 0 (zero) when Yis nitrogen and thus there are no non-hydrogen substituents. When "e" is1 and Y is nitrogen, the R₄ substituent may be located on any of theavailable carbon atoms of the pyridobenz moiety of the pyridobenzoxazineportion of the compound, i.e., at the 5', 6', 8', 9' or 10' positions,more usually at the 8', 9' or 10' positions. When "e" is 2, the R₄substituent may be the same or different and, in either case, areselected from the above-described group and are located at two ofaforedescribed available carbon atoms.

R₉ in graphic formula IV is selected from the group consisting ofhydrogen, halogen, e.g,, chloro, fluoro or bromo, C₁ -C₅ alkyl, e.g., C₁-C₂ alkyl, C₁ -C₅ alkoxy, e.g., C₁ -C₂ alkoxy, C₁ -C₄ monohaloalkyl,e.g., C₁ -C₂ monohaloalkyl such as chloromethyl, chloroethyl andfluoromethyl, C₁ -C₂ polyhaloalkyl, as for example trihaloalkyl such astrichloroalkyl or trifluoroalkyl, e.g., trifluoromethyl, cyano and C₁-C₈ alkoxycarbonyl. The R'₉ substituent may be located at either thenumber 4 or 5 carbon atom positions.

R₆ in graphic formula IV is selected from the group consisting ofhalogen, e.g., chloro, fluoro or bromo, C₁ -C₅ alkyl, e.g., C₁ -C₂alkyl, C₁ -C₅ alkoxy, e.g., C₁ -C₂ alkoxy, cyano, C₁ -C₈ alkoxycarbonyl,C₁ -C₂ polyhaloalkyl, C₁ -C₄ monohaloalkyl and monoalkylamino ordialkylamino wherein the alkyl moiety of the alkylamino group containsfrom 1 to 4 carbon atoms, e.g., methylamino, ethylamino, propylamino anddiethylamino.

The letter "c" in formula IV is an integer of from 0 to 2, e.g., 0 or 1,more typically 0. When there are substituents on the benz moiety of thebenzindoline portion of the depicted molecule and the letter "c" is 1 or2, it denotes the number of non-hydrogen substituents. When "c" is 1,the R₆ substituent may be located at the number 6, 7 or 8 carbon atoms.Similarly, when "c" is 2, the R₆ substituents may be present at the 6and 7, 6 and 8, or 7 and 8 carbon atoms.

Of particular interest, are photochromic materials represented bygraphic formulae IVA and IVB wherein Y is nitrogen; R₁ is a C₁ -C₄alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, secondarybutyl, isobutyl and tertiary butyl; R₂ and R₃ are each methyl, ethyl orphenyl; R₄ is selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy, chloro, fluoroor cyano; R₉ is selected from hydrogen, fluoro, trifluoromethyl and C₁-C₄ alkyl; R₆ is selected from C₁ -C₄ alkyl, C₁ -C₄ alkoxy, chloro,fluoro and C₁ -C₄ monoalkylamino or dialkylamino; "c" is 0 or 1; and "e"is 0 or 1.

Examples of contemplated compounds within the scope of graphic formulaeIVA and IVB are listed in Tables III and IV. In Table III, Y is carbon.In Table IV, Y is nitrogen. Compound 1 of Table III may be named:9'-methoxy-1,3,3-trimethylspiro [benz[e]indolino-2,3'[3H]naphth[2,1-b][1,4]oxazine]. Other compounds in Table III and the compounds ofTable IV may be similarly named as substituted spiro benz(indolino)naphthoxazines or spiro benz(indolino) pyrido benzoxazines using thesubstituents described in the Tables for such compounds or thesubstituents described with respect to graphic formula IV. In namingsuch compounds herein, the IUPAC rules of organic nomenclature have beenused. Carbon atom numbering in the compounds is in accordance with thenumbering sequence illustrated in graphic formulae IVA' and IVB'. Ahyphen (-) indicates the absence of a non-hydrogen substituent.

                                      TABLE III                                   __________________________________________________________________________    SUBSTITUENT (Y = C)                                                           Compound/                                                                            R.sub.1 R.sub.2                                                                          R.sub.3                                                                          R.sub.4                                                                             R.sub.9                                                                            R.sub.6                                                                           Face                                      __________________________________________________________________________     1     Me      Me Me 9'-OMe                                                                               --   -- e                                          2     Me      Me Me 9'-OMe                                                                               --   -- g                                          3     Et      Me Me 9'-OMe                                                                               --   -- e                                          4     n-Pr    Me Me 9'-OMe                                                                               --   -- e                                          5     i-Pr    Me Me 9'-OMe                                                                               --   -- e                                          6     Et      Me Me 9'-OMe                                                                               --   -- g                                          7     n-Pr    Me Me 9'-OMe                                                                               --   -- g                                          8     Me      Me Me 9'-OMe                                                                              5-F   -- e                                          9     Me      Me Me 9'-OMe                                                                              5-CF.sub.3                                                                          -- e                                         10     Me      Me Me 9'-OMe                                                                              5-F   -- g                                         11     Me      Me Me 9'-OMe                                                                              5-CF.sub.3                                                                          -- g                                         12     Me      Me Ph 9'-OMe                                                                               --  7-Cl                                                                              g                                         13     Me      Me Me (OMe).sub.2                                                                         5-OMe                                                                               -- g                                         14     Et      Me Me 6'-NEt.sub.2                                                                         --  OMe e                                         15     Me      Me Me 9'-OMe                                                                              5-Me 6-Me                                                                              g                                         16     Me      Me Me 9'-Me 5-Me 6-Me                                                                              e                                         17     Me      Me Me 8'-NO.sub.2                                                                         5-CF.sub.3                                                                          -- g                                         18     Me      Me Me 8'-Cl  --   -- e                                         19     i-Pr    Me Me 8'-CF.sub.3                                                                          --   -- e                                         20     Me      Me Me 8'-ClMe                                                                             5-CF.sub.3                                                                          -- g                                         21     Me      Me Me 9'-OMe                                                                              5-AcO                                                                               -- g                                         22     Me      Me Me 9'-OMe                                                                              5-ClMe                                                                             7-Cl                                                                              e                                         23     Me      Me Me  --    --   -- e or g                                    24     Me      Me Me 9'-OEt                                                                               --   -- e or g                                    25     Me      Me Me 8'-Br  --   -- e or g                                    26     (CH.sub.2).sub.2 CN                                                                   Me Me 9'-OMe                                                                               --   -- e or g                                    27     (CH.sub.2).sub.2 COOH                                                                 Me Me 9'-OMe                                                                               --   -- e or g                                    28     (CH.sub.2).sub.2 OH                                                                   Me Me 9'-OMe                                                                               --   -- e or g                                    29     Me      Me Me 9'-OMe                                                                               --  7-CF.sub.3                                                                        e                                         30     (CH.sub.2).sub.2 OCH.sub.3                                                            Me Me 9'-OMe                                                                               --   -- e                                         __________________________________________________________________________

                                      TABLE IV                                    __________________________________________________________________________    SUBSTITUENT (Y = N)                                                           Compound/                                                                            R.sub.1 R.sub.2                                                                          R.sub.3                                                                          R.sub.4                                                                             R.sub.9                                                                            R.sub.6                                                                           Face                                      __________________________________________________________________________     1     Me      Me Me  --    --   -- e                                          2     Me      Me Me  --    --   -- g                                          3     Me      Me Me 6'-Me  --   -- e or g                                     4     Me      Me Me 6'-OMe                                                                               --   -- e or g                                     5     Me      Me Me 6'-Cl  --   -- e or g                                     6     Me      Me Me  --   5-F   -- e or g                                     7     Me      Me Me  --   5-CF.sub.3                                                                          -- e or g                                     8     Et      Me Me  --    --   -- e or g                                     9     n-Pr    Me Me  --    --   -- e or g                                    10     i-Pr    Me Me  --    --   -- e                                         11     Me      Me Et 6'-Me 5-CF.sub.3                                                                         7-F g                                         12     Me      Me Me 6'-OMe                                                                              5-Me 6-Me                                                                              g                                         13     Me      Me Et 6'-OMe                                                                               --  6-OMe                                                                             g                                         14     Me      Me Me 6'-OMe                                                                              5-F  6-NEt.sub.2                                                                       g                                         15     Me      Me Et 6'-F  5-F  6-Me                                                                              g                                         16     Me      Me Me 6'-Me  --   -- e or g                                    17     (CH.sub.2).sub.2 CN                                                                   Me Me  --    --   -- e or g                                    18     (CH.sub.2).sub.2 COOH                                                                 Me Me  --    --   -- e or g                                    19     (CH.sub.2).sub.2 OH                                                                   Me Me  --    --   -- e or g                                    20     Me      Me Me  --    --  7-CF.sub.3                                                                        e or g                                    21     Me      Me Me  --    --  7-F e or g                                    __________________________________________________________________________     Key For Tables:                                                               Me = methyl                                                                   Et = ethyl                                                                    nPr = npropyl                                                                 iPr = isopropyl                                                               (CH.sub.2).sub.2 CN = cyanoethyl                                              (CH.sub.2).sub.2 COOH = carboxyethyl                                          Ph = phenyl                                                                    OMe = methoxy                                                                NO.sub.2 = nitro                                                              NEt.sub.2 = diethylamino                                                      (CH.sub.2).sub.2 OH = hydroxyethyl                                            (CH.sub.2).sub.2 OCH.sub.3 = methoxyethyl                                     CF.sub.3 = trifluoromethyl                                                    ClMe = chloromethyl                                                           Cl = chlorine                                                                 F = fluorine                                                                  AcO = acetoxy                                                            

The described photochromic substances of Group I may be synthesized byreaction of the corresponding (R₅)_(d) --substituted indoline (Fischer'sbase) or indolium salt, e.g., the iodide salt, with the corresponding(R₄)_(e) --substituted-1-nitroso-2-naphthol or (R₄)_(e)--substituted-5-nitroso-6-quinolinol.

Photochromic substances represented by graphic formula IV are thesubject of co-pending, co-assigned U.S. patent application Ser. No.78,325, filed July 27, 1987. That application, and particularly themethods described therein for preparing the aforesaid compounds, isincorporated herein by reference.

Photochromic substances that have at least one activated absorptionmaximum between about 400 and less than 590 nanometers includespiro(indolino) benzoxazine compounds that may be represented by thefollowing graphic formula V: ##STR7## In the above graphic formula V,R₁, R₂ and R₃ are the same as that described with respect to graphicformula I.

R₈ in graphic formula V may be selected from the group consisting of C₁-C₅ alkyl, halogen, e.g., chloro and fluoro, C₁ -C₅ alkoxy, nitro,cyano, C₁ -C₄ monohaloalkyl, C₁ -C₄ polyhaloalkyl, e.g., trihaloalkyl,C₁ -C₈ alkoxycarbonyl, and C₁ -C₄ acyloxy. e.g., acetoxy. While anyhalogen, i.e., chlorine, bromine, iodine and fluorine, may be used inrespect to the halogen or haloalkyl substituents, chlorine, fluorine andbromine, especially chlorine and fluorine is preferred for the halogensubstituent and fluorine is preferred for the polyhaloalkyl substituent,e.g., trifluoromethyl (CF₃). Preferably, R₈ may be selected from thegroup consisting of C₁ -C₂ alkyl, chlorine, fluorine, C₁ -C₂trihaloalkyl, e.g., trihalomethyl such as trifluoromethyl, and C₁ -C₅alkoxy.

The letter "h" in formula V is an integer from 0 to 4, e.g., 0 to 2,such as 1 or 2. When "h" is 2 or more, the R₈ substituents may be thesame or different and in either case are selected from theaforedescribed group. The R₈ substituents(s) may be located on any ofthe available carbon atoms of the indolino portion of the compound,i.e., at the 4', 5', 6', or 7' positions. When "h" is 2, the R₈substituents may be present at the 4' and 5', 5' and 6', 4' and 7', 6'and 7' carbon atoms of the indolino moiety.

As described with respect to graphic formulae II and III, it is possiblethat the photochromic organic compounds represented by graphic formula Vmay be a mixture of isomers due to the alternative directional mechanismby which intramolecular condensation occurs during formation of thestarting indole reactant (Fischer's base). That discussion is equallyapplicable to compounds of graphic formula V and is incorporated hereinby reference.

R₇ in graphic formula V is selected from the group consisting ofhalogen, e.g., chloro, fluoro, or bromo, C₁ -C₄ alkyl, C₁ -C₅ alkoxy,nitro, cyano, thiocyano, C₁ -C₄ monohaloalkyl, e.g., chloromethyl andchloroethyl, C₁ -C₂ polyhaloalkyl, e.g., trihaloalkyl, such astrifluoromethyl and 2,2,2-trifluoroethyl, and monoalkylamino ordialkylamino wherein the alkyl moiety of the alkylamino group containsfrom 1 to 4 carbon atoms, e.g., methylamino, dimethylamino anddiethylamino. The letter "g" in formula V is an integer of from 1 to 4,usually, 1, 2, or 3, and preferably is 1 or 2. In particular, R₇ is C₁-C₂ alkyl, C₁ -C₂ alkoxy, chloro, bromo, nitro, or trifluoromethyl.

The R₇ substituent (when "g" is 1) may be located on any of theavailable carbon atoms of the benzene ring of the benzoxazine moiety ofthe compound, i.e., at the 5, 6, 7 or 8 positions. Preferably, the R₇substituent is present on the 5, 6, or 7 carbon atoms of the benzenering of the benzoxazine moiety. When "g" is 2 or more, the R₇substituents may be the same or different and in either case areselected from the above-described group. When "g" is 2, the R₇substituents may be located at the 5 and 6, 5 and 7, 5 and 8, 6 and 7, 7and 8 or 6 and 8 positions; preferably at the 5 and 7 positions. When"g" is 3, the R₇ substituents may be located at the 5, 6, and 7; 5, 7,and 8; 6, 7, and 8; or 5, 6, and 8 positions.

Of particular interest, are photochromic materials represented bygraphic formula V wherein R₁ is a C₁ -C₄ alkyl, such as methyl, ethyl,n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl and tertiarybutyl; R₂ and R₃ are each methyl, ethyl or phenyl; R₈ is selected fromtrifluoromethyl, chlorine, fluorine, methyl or methoxy; R₇ is selectedfrom methoxy, methyl, nitro, fluoro, bromo or chloro, "h" is 1 or 2, and"g" is 1 or 2.

Examples of contemplated compounds within the scope of graphic formula Vare listed in Table V. The prime (') designations for the R₈ substituentpositions in Table V have been omitted. A hyphen (-) indicates theabsence of a non-hydrogen substituent. Compound 1 may be named:7-methoxy-1',3',3',4'(and 6'), 5'-pentamethylspiro[2H-1,4-benzoxazine-2,2'-indoline]. Compounds 2-44 may be similarlynamed as substituted spiro(indolino) benzoxazines using the substituentsdescribed in Table V for such compounds. In naming thespiro(indoline)benzoxazines, the IUPAC rules of organic nomenclaturehave been used. The positions on the indoline portion of the moleculehave been numbered counterclockwise starting with the nitrogen atom asnumber one (1), and are identified by a prime number, e.g., 3'. Thepositions on the benzoxazine portion of the molecule have been numberedclockwise starting with the oxygen atom as number one (1).

                                      TABLE V                                     __________________________________________________________________________    SUBSTITUENT                                                                   Compound/                                                                             R.sub.1                                                                           R.sub.2                                                                          R.sub.3                                                                           R.sub.8                                                                            R.sub.8                                                                           R.sub.7                                                                            R.sub.7                                      __________________________________________________________________________     1      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              7-OMe                                                                               --                                           2      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              7-OMe                                                                              5-OMe                                         3      Me  Me Me  5-OMe                                                                               -- 7-OMe                                                                              5-OMe                                         4      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              7-OMe                                                                              5-Cl                                          5      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              6-NO.sub.2                                                                          --                                           6      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              6-Cl  --                                           7      Me  Me Ph   --   -- 7-OMe                                                                               --                                           8      Me  Me Et   --   -- 7-OMe                                                                              5-OMe                                         9      n-Bu                                                                              Me Me   --   -- 7-OMe                                                                              5-OMe                                        10      Me  Cyclohexyl                                                                            --   -- 7-OMe                                                                              5-OMe                                        11      Me  Me Me  5-OMe                                                                               -- 6-NO.sub.2                                                                          --                                          12      Me  Me Me  5-OMe                                                                               -- 6-NO.sub.2                                                                         8-OMe                                        13      Et  Me Me  5-OMe                                                                               -- 6-NO.sub.2                                                                         8-OMe                                        14      Me  Me Et  4(6)-Me                                                                            5-Me                                                                              6-NO.sub.2                                                                         8-OMe                                        15      Me  Me Ph   --   -- 6-NO.sub.2                                                                         8-OMe                                        16      Me  Me Me  4(6)-Me                                                                            5-Me                                                                              8-NO.sub.2                                                                         6-OMe                                        17      Me  Me Me   --   -- 8-NO.sub.2                                                                         6-OMe                                        18      Me  Me Me  5-OMe                                                                               -- 8-NO.sub.2                                                                         6-OMe                                        19      Et  Me Me   --   -- 7-OMe                                                                              6-Br                                         20      Me  Me Et  4(6)-Me                                                                            5-Me                                                                              7-OMe                                                                              5-Me                                         21      i-Pr                                                                              Me Me  5-OMe                                                                               -- 7-OMe                                                                              5-OMe                                        22      Me  Me Me   --   -- 7-NEt.sub.2                                                                         --                                          23      Benzyl                                                                            Me Me   --   -- 7-NO.sub.2                                                                          --                                          24      Me  Me Me  4(6)-F                                                                              -- 7-OMe                                                                              5-OMe                                        25      Me  Me Me  6-Cl  -- 7-OMe                                                                              5-OMe                                        26      Me  Me Me  7-F   -- 7-OMe                                                                              5-OMe                                        27      Me  Me Me  7-Cl  -- 7-OMe                                                                              5-OMe                                        28      Me  Me Me  7-Br  -- 7-OMe                                                                              5-OMe                                        29      Me  Me Me  5-F   -- 7-OMe                                                                              5-OMe                                        30      Me  Me Me  5-Cl  -- 7-OMe                                                                              5-OMe                                        31      Me  Me Me  5-OMe                                                                               -- 7-OMe                                                                              5-OMe                                        32      Me  Me Me  5-OMe                                                                               -- 7-OMe                                                                               --                                          33      Me  Me Me  6-CF.sub.3                                                                          -- 7-OMe                                                                              5-OMe                                        34      Me  Me Et  4(6)-F                                                                              -- 7-OMe                                                                              5-OMe                                        35      Me  Me Me  4(6)AcO                                                                             -- 7-OMe                                                                              5-OMe                                        36      Me  Me Me  4(6)CF.sub.3                                                                        -- 7-OMe                                                                              5-OMe                                        37      Me  Me Me  4(6)F                                                                              5-F 7-OMe                                                                              5-OMe                                        38      Me  Me Me  4(6)Cl                                                                             5-Cl                                                                              7-OMe                                                                              5-OMe                                        39      Me  Me Me  4(6)F                                                                               -- 7-OMe                                                                              5-Cl                                         40      Me  Me Me  4(6)F                                                                               -- 7-OMe                                                                              5-F                                          41      Me  Me Me  4(6)AcO                                                                             -- 7-OMe                                                                              5-OMe                                        42      Me  Me Me   --  5-AcO                                                                             7-OMe                                                                              5-OMe                                        43      Me  Me Me  4(6)AcO                                                                            5-F 7-OMe                                                                              5-OMe                                        44      Me  Me Me  4(6)AcO                                                                            5-Cl                                                                              7-OMe                                                                              5-OMe                                        45      CNEt                                                                              Me Me   --   -- 7-OMe                                                                              5-OMe                                        46      Me  Me Et  5-Cl 6-Me                                                                              7-OMe                                                                              5-OMe                                        __________________________________________________________________________     Key:                                                                          Me = methyl                                                                   nBu = nbutyl                                                                  Et = ethyl                                                                    iPr = isopropyl                                                               CNEt = cyanoethyl                                                             Ph = phenyl                                                                   OMe = methoxy                                                                 NO.sub.2 = nitro                                                              NEt.sub.2 = diethylamino                                                      Br =  bromine                                                                 Cl = chlorine                                                                 F = fluorine                                                                  AcO = acetoxy                                                            

The photochromic substances or compositions described herein may bedissolved in common organic solvents such as benzene, toluene,chloroform, ethylacetate, methyl ethyl ketone, acetone, ethyl alcohol,methyl alcohol, acetonitrile, tetrahydrofuran, dioxane, methyl ether ofethylene glycol, dimethylformamide, dimethylsulfoxide, methylCellosolve, morpholine and ethylene glycol. They may also be dispersedin liquids containing water and/or alcohols.

The photochromic substances or compositions used in the practice of thepresent invention may also be dissolved in colorless or transparentsolutions prepared from transparent organic host materials, e.g.,transparent polymers (or copolymers) or blends of such transparentpolymers and optionally a suitable organic solvent, e.g., polymers oftransparent organic host materials described hereinafter dissolved inone or more of the aforesaid described organic solvents. Examples ofsuch solutions include a poly(vinyl acetate)-acetone solution, anitrocellulose-acetonitrile solution, a poly(vinyl chloride)-methylethyl ketone solution, a poly(methyl methacrylate)-acetone solution, acellulose acetate-dimethylformamide solution, a poly(vinylpyrrolidone)acetonitrile solution, a polystyrene-benzene solution and anethyl cellulose-methylene chloride solution. The aforesaid photochromicsolutions or compositions may be applied to a compatible host material,e.g., a transparent support, such as cellulose triacetate, polyethyleneterephthalate or baryta paper and dried to obtain an article that may becolor formed by ultraviolet radiation and returned to colorless byremoving the source of ultraviolet radiation.

The photochromic substances described herein (or compositions containingthem) may be applied to or incorporated within a coating compositionapplied to a compatible support; or applied to or incorporated withinthe article comprising the compatible host, e.g., a polymerized organicmaterial such as a synthetic polymeric plastic host material.

The polymer host material will usually be transparent, but may betranslucent or even opaque. The polymer product need only be transparentto that portion of the electromagnetic spectrum, which activates thephotochromic substance, i.e., that wavelength of ultraviolet (UV) lightthat produces the open form of the substance and that portion of thevisible spectrum that includes the absorption maximum wavelength of thesubstance in its UV activated form, i.e., the open form. Further, theresin color should not be such that it masks the color of the activatedform of the photochromic substance, i.e., so the change in color isreadily apparent to the observer.

Preferably, the host material article is a solid transparent material oran optically clear material, e.g., materials suitable for ophthalmicelements, such as ophthalmic lenses, or materials useful forapplications such as windows, windshields, aircraft transparencies, etc.A host material containing the photochromic substances described inconnection with the present invention can be used in the preparation ofphotochromic plastic films, sheets and lenses, such as lenses forsunglasses, ski goggles, visors, camera lenses and variable densityfilters. As used herein, the term "optical element" is meant to includelenses and transparencies. The photochromic substances or compositionsdescribed herein also may be incorporated into coatings such as paints,inks, etc. by admixing the material with the fluid coating compositionbefore it is applied to the host surface and dried.

Examples of host materials which may be used with the photochromicsubstances or compositions described herein include: homopolymers andcopolymers of polyol(allyl carbonate) monomers, homopolymers andcopolymers of polyfunctional acrylate monomers, polyacrylates,poly(alkylacrylates) such as poly(methyl methacrylate), celluloseacetate, cellulose triacetate, cellulose acetate propionate, celluloseacetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), poly(vinylchloride), poly(vinylidene chloride), polyurethanes, polycarbonates,poly(ethylene terephthalate), polystyrene, copoly(styrene-methylmethacrylate) copoly(styrene-acrylonitrile), polyvinylbutyral andhomocopolymers and copolymers of diallylidene pentaerythritol,particularly copolymers with polyol (allyl carbonate) monomers, e.g.,diethylene glycol bis(allyl carbonate), and acrylate monomers.Transparent copolymers and blends of the transparent polymers are alsosuitable as host materials. Preferably, the host material is anoptically clear polymerized organic material prepared from apolycarbonate resin, such as the carbonate-linked resin derived frombisphenol A and phosgene, which is sold under the trademark, LEXAN; apoly(methyl methacrylate), such as the material sold under thetrademark, PLEXIGLAS: polymerizates of a polyol(allyl carbonate),especially diethylene glycol bis(allyl carbonate), which monomer is soldunder the trademark CR-39, and its copolymers with for example vinylacetate, e.g., copolymers of from 80-90 percent diethylene glycolbis(allyl carbonate) and 10-20 percent vinyl acetate; particularly 80-85percent of the bis(allyl carbonate) and 15-20 percent vinyl acetate,cellulose acetate, cellulose propionate, cellulose butyrate, polystyreneand its copolymers with methyl methacrylate, vinyl acetate andacrylonitrile, and cellulose acetate butyrate.

Polyol (allyl carbonate) monomers which can be polymerized to form atransparent host material are the allyl carbonates of linear or branchedaliphatic or aromatic liquid polyols, e.g., aliphatic glycol bis(allylcarbonate) compounds, or alkylidene bisphenol bis(allyl carbonate)compounds. These monomers can be described as unsaturated polycarbonatesof polyols, e.g, glycols. The monomers can be prepared by procedureswell known in the art, e.g., U.S. Pat. Nos. 2,370,567 and 2,403,113.

The polyol (allyl carbonate) monomers can be represented by the graphicformula: ##STR8## wherein R is the radical derived from an unsaturatedalcohol and is commonly an allyl or substituted allyl group, R' is theradical derived from the polyol, and n is a whole number from 2 - 5,preferably 2. The allyl group (R) can be substituted at the 2 positionwith a halogen, most notably chlorine or bromine, or an alkyl groupcontaining from 1 to 4 carbon atoms, generally a methyl or ethyl group.The R group can be represented by the graphic formula: ##STR9## whereinR_(o) is hydrogen, halogen, or a C₁ -C₄ alkyl group. Specific examplesof R include the groups: allyl, 2-chloroallyl, 2-bromoallyl,2-fluoroallyl, 2-methallyl, 2-ethylallyl, 2-isopropylallyl,2-n-propylallyl, and 2-n-butylallyl. Most commonly R is the allyl groupH₂ C═CH-CH₂ --.

R' is a polyvalent radical derived from the polyol, which can be analiphatic or aromatic polyol that contains 2, 3, 4 or 5 hydroxy groups.Typically, the polyol contains 2 hydroxy groups, i.e., a glycol orbisphenol. The aliphatic polyol can be linear or branched and containfrom 2 to 10 carbon atoms. Commonly, the aliphatic polyol is an alkyleneglycol having from 2 to 4 carbon atoms or a poly(C₂ -C₄) alkyleneglycol, i.e., ethylene glycol, propylene glycol, trimethylene glycol,tetramethylene glycol, or diethylene glycol, triethylene glycol, etc.

The aromatic polyol can be represented by the graphic formula: ##STR10##wherein A is a bivalent radical derived from an acyclic aliphatichydrocarbon, e.g., an alkylene or alkylidene radical, having from 1 to 4carbon atoms, e.g., methylene, ethylene, and dimethylmethylene(isopropylidene:), Ra represents lower alkyl substituents of from 1 to 3carbon atoms and halogen, e.g., chlorine and bromine, and p is 0, 1, 2,or 3. Preferably, the hydroxyl group is in the ortho or para position.

Specific examples of the radical R' include: alkylene groups containingfrom 2 to 10 carbon atoms such as ethylene, (--CH₂ --CH₂ --),trimethylene, methylethylene, tetramethylene, ethylethylene,pentamethylene, hexamethylene, 2-methylhexamethylene, octamethylene, anddecamethylene; alkylene ether groups such as --CH₂ --O--CH₂ --, --CH₂CH₂ --O--CH₂ CH₂ --, --CH₂ --O--CH₂ --CH₂ --, and --CH₂ CH₂ CH₂ --O--CH₂CH₂ CH₂ --; alkylene polyether groups such as --CH₂ CH₂ --O--Ch₂ CH₂--O--CH₂ CH₂ --, and --CH₂ CH₂ CH₂ --O--CH₂ CH₂ CH₂ --O--CH₂ CH₂ CH₂ --;alkylene carbonate and alkylene ether carbonate groups such as --CH₂ CH₂--O--CO--O--CH₂ CH₂ -- and --CH₂ CH₂ --O--CH₂ CH₂ --O--CO--O--CH₂ CH₂--O--CH₂ CH₂ --;and isopropylidene bis(para-phenyl), ##STR11## Mostcommonly, R' is --CH₂ CH₂ --, --CH₂ CH₂ --O--CH₂ CH₂ --, or --CH₂ CH₂--O--CH₂ CH₂ --O--CH₂ Ch₂ --.

Specific examples of polyol (allyl carbonate) monomers include ethyleneglycol bis(2-chloroallyl carbonate), ethylene glycol bis(allylcarbonate), diethylene glycol bis(2-methallyl carbonate), diethyleneglycol bis(allyl carbonate), triethylene glycol bis(allyl carbonate),propylene glycol bis(2-ethylallyl carbonate), 1,3-propanediol bis(allylcarbonate), 1,3-butanediol bis(allyl carbonate), 1,4-butanediolbis(2-bromoallyl carbonate), dipropylene glycol bis(allyl carbonate),trimethylene glycol bis(2-ethylallyl carbonate), pentamethylene glycolbis(allyl carbonate), and isopropylidene bisphenol bis(allyl carbonate).

Industrially important polyol bis(allyl carbonate) monomers which can beutilized in the invention herein contemplated are: ##STR12## Diethyleneglycol bis(allyl carbonate) is preferred.

Because of the process by which the polyol(allyl carbonate) monomer isprepared, i.e., by phosgenation of the polyol (or allyl alcohol) andsubsequent esterification by the allyl alcohol (or polyol), the monomerproduct can contain related monomer species in which the moietyconnecting the allyl carbonate groups contains one or more carbonategroups. These related monomer species can be represented by the graphicformula: ##STR13## wherein R is as defined above, R_(b) is a bivalentradical, e.g., alkylene or phenylene, derived from a diol, and s is awhole number from 2 to 5. The related monomer species of diethyleneglycol bis(allyl carbonate) can be represented by the graphic formula,##STR14## wherein s is a whole number from 2 to 5. The polyol (allylcarbonate) monomer can typically contain from 2 to 20 weight percent ofthe related monomer species and such related monomer species can bepresent as mixtures, i.e., mixtures of the species represented by sbeing equal to 2, 3, 4 etc.

In addition, a partially polymerized form of the polyol (allylcarbonate) monomer, i.e., prepolymer, can be used. In that embodiment,the monomer is thickened by heating or partially polymerized by usingsmall, e.g., 0.5-1.5 parts of initiator per hundred parts of monomer(phm), to provide a non-gel containing, more viscous monomeric material.

As used in the present description and claims, the term polyol(allylcarbonate) monomer or like names, e.g., diethylene glycol bis(allylcarbonate), are intended to mean and include the named monomer orprepolymer and any related monomer species contained therein.

Polyfunctional acrylate monomers that may be used to prepare syntheticpolymeric host materials are esterification products of an acrylic acidmoiety selected from the group consisting of acrylic acid andmethacrylic acid, and a polyol, e.g., a diol, a triol or tetracarbinol.More particularly, the polyfunctional acrylate monomer may berepresented by the following graphic formula:

    (CH.sub.2 ═C(R.sub.t)--C(O)).sub.n R"                  (XI)

wherein R_(t) is hydrogen or methyl, n is the number 2, 3, or 4, and R"is the multivalent radical, i.e., a bivalent, trivalent or quadravalentradical, remaining after removal of the hydroxy groups from a polyol,having from 2 to 4 hydroxy groups, e.g., a diol, a triol ortetracarbinol respectively. More particularly, R_(t) is hydrogen ormethyl, and n is 2 or 3, more usually 2.

R" may be selected from the group consisting of alpha, omega C₂ -C₈glycols, cyclohexane diol, diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, C₂ -C₅ triols andpentaerythritol. Examples of such polyols include ethylene glycol,trimethylene glycol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexane diol,propylene glycol, trimethylol propane, glycerol and the like.

Examples of polyfunctional acrylate monomers, such as diacrylates andtriacrylates, include: ethylene glycol diacrylate, ethylene glycoldimethyacrylate, 1,2-propane diol diacrylate, 1,3-propane dioldiacrylate, 1,2-propane diol dimethacrylate, 1,3-propane dioldimethacrylate, 1,4-butane diol diacylate, 1,3-butane dioldimethyacrylate, 1,4-butane diol dimethacrylate, 1,5-pentane dioldiacrylate, 2,5-dimethyl-1,6-hexane diol dimethacrylate, diethyleneglycol diacrylate, diethylene glycol dimethacrylate, triethylene glycoldimethacrylate, trimethylol propane trimethacrylate, tetraethyleneglycol diacrylate, tetraethylene glycol dimethacrylate, dipropyleneglycol diacrylate, dipropylene glycol dimethacrylate, trimethylolpropane triacrylate, glycerol triacrylate, glycerol trimethacrylate,pentaerythritol triacrylate, pentaerythritol dimethacrylate,pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate andmixtures of such acrylate monomers.

A portion of the polyfunctional acrylate monomer may be replaced with amonofunctional copolymerizable monomer containing the vinyl (CH₂ ═CH--)grouping. Such compatible monomers include monofunctional acrylic andmathacrylic acid esters, and vinyl esters of C₂ -C₆ carboxylic acids,i.e., vinyl carboxylates. Preferably, the copolymerizable monomer is anon-aromatic, e.g., non-benzenoid, containing monomer. Monofunctionalacrylic or methacrylic ester monomers may be graphically illustrated bythe following formula,

    CH═ C(R.sub.t)--C(O)--O--R"'                           (XII)

wherein R_(t) is hydrogen or methyl, and R"' is selected from the groupconsisting of C₁ -C₁₂, e.g., C₁ -C₈, alkyl, C₅ -C₆ cycloalkyl, glycidyland hydroxyethyl. Preferably, R"' is a a C₁ -C₄ alkyl, e.g., methyl orcyclohexyl.

Examples of monofunctional acrylic acid type monomers include, forexample, the acrylic and methacrylic acid esters of alkanols such asmethanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol andoctanol, e.g., methyl acrylate, methyl methacrylate, ethyl acrylate andethyl methacrylate, cycloalkanols such as cyclopentanol andcyclohexanol, glycidol (3-hydroxy propylene oxide, (d, 1, dl)) andethylene glycol. Examples of vinyl carboxylates include vinyl acetate,vinyl propionate, vinyl butyrate and vinyl valerate In addition toand/or in place of the aforedescribed monofunctional copolymerizablemonomer, monofunctional allylic and difunctional allylic copolymerizablecompatible monomers may also replace a portion of the polyfunctionalacrylate monomer. Monofunctional allylic monomers contemplated includeallyl esters of C₂ -C₆ carboxylic acids, C₁ -C₆ allyl ethers and othercopolymerizable allyl compounds. Preferably the monofunctional allylicmonomer is a non-aromatic compound Difunctional allylic copolymerizablemonomers contemplated herein are the polyol (allyl carbonates) monomersof graphic formula VI.

The amount of photochromic substance or composition-containing sameapplied to or incorporated into a host material is not critical providedthat a sufficient amount is used to produce a photochromic effectdiscernible to the naked eye. Generally such amount can be described asa photochromic amount. The amount used depends often upon the intensityof color desired upon irradiation thereof and upon the method used toincorporate or apply the photochromic substances. Typically, the morecompound applied or incorporated, the greater is the color intensity.Usually, the amount of each photochromic substance incorporated into orapplied to the host material ranges from about 0.01 to about 20 percentby weight, more usually from about 0.05 to about 10 percent by weight,based on the weight of the host material. Stated another way, the amountof each photochromic substance used to impart a photochromic effect willtypically vary from about 0.1 to about 10, e.g., 0.5 to 2 milligrams ofthe photochromic substance per square inch of the surface of the hostmaterial independent of the thickness of the host material article.Hence, the photochromic substance is present in higher concentrations inthin samples, films, or coatings, and in lower concentrations in thicksamples.

The present invention is more particularly described in the followingexamples which are intended as illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art.

EXAMPLE 1

A mixture of photochromic substances was prepared by combining 0.0102grams of 9'-methoxy-1,3,3-trimethylspiro[benz[g]indolino-2,3'[3H]naphth[2,1-b][1,4]oxazine]and 0.0886 grams of5,7-dimethoxy-1',3'-dimethyl-3'-ethyl-4'(and 6')fluorospiro[2H-1,4-benzoxazine-2,2'-indoline] with 1.0 milliliters ofdiglyme to form a solution of the aforesaid photochromic substances.This solution was placed in a vial and a 1 square centimeter sample of aslightly undercured polymer of diethylene glycol bis(allyl carbonate)was immersed in the solution. The vial was placed in an oven maintainedat about 100° C. for about 90 minutes. The plastic sample was removedfrom the vial and rinsed with methyl ethyl ketone. The dried plastictest sample was irradiated with 365 nanometer ultraviolet light and thesample changed from colorless to a purple-gray color.

A small sample of a cast sheet (1 centimeter ×1 centimeter×1/32 inch[0.08 centimeter]) prepared from about 80 percent diethylene glycolbis(allyl carbonate) and 20 percent vinyl acetate was immersed in thesame photochromic solution and placed in a 100° C. oven for three andone-half hours. Upon irradiation with ultraviolet light, the samplechanged from colorless to purple-gray.

EXAMPLE 2

The procedure of Example 1 was followed using 0.0803 grams of5,7-dimethoxy-1',3',3'-trimethyl-4'(and6')-fluorospiro[2H-1,4-benzoxazine-2,2'-indoline] and 0.0118 grams ofthe spiro(indolino) naphthoxazine substance of Example 1. A small testsample of the polymer prepared from about 80 percent diethylene glycolbis(allyl carbonate) and 20 percent vinyl acetate was immersed in thesolution and placed in a 100° C. oven for 90 minutes. The plastic samplewas removed from the solution, rinsed with methyl ethyl ketone andirradiated with ultraviolet light. The sample became light gray with aslight purple background.

EXAMPLE 3

The procedure of Example 1 was followed utilizing a solution preparedfrom 0.0997 grams of the spiro(indolino) benzoxazine compound of Example1 and 0.0047 grams of9'-methoxy-1,3,3-trimethylspiro[benz[e]indolino-2,3'[3H]naphth[2,1-b[[1,4]oxazine]and 1.5 milliliters of diglyme. A small piece of a plastic test sample(about 1/2 inch×1/2 inch×1/32 inch [1.27 cm.×1.27 cm.×0.08 cm.])prepared from about 80 percent diethylene glycol bis(allyl carbonate)and 20 percent vinyl acetate was immersed in the solution and placed ina 155° C. oven for 21/2 hours. The vial containing the plastic testsample was cooled to room temperature. The sample was removed from thevial, rinsed with methyl ethyl ketone and dried. Upon irradiation with365 nanometer ultraviolet light, the sample changed form colorless togray.

EXAMPLE 4

A solution of the photochromic substances of Example 3 was preparedusing 0.041 grams of the spiro(indolino) benzoxazine compound and 0.0085grams of the spiro(benzindolino) naphthoxazine compound and 1 milliliterof methylene chloride. A piece of Balston No. 50 filter paper wassaturated with the solution and allowed to air dry for 2 hours. Thepaper was then placed on a 4 centimeter by 4 centimeter by 0.08centimeter thick piece of a plastic test sample prepared from about 80percent diethylene glycol bis(allyl carbonate) and 20 percent vinylacetate. A piece of untreated filter paper was placed on the other sideof the plastic sample and the sandwich placed between two plates oftempered glass. The entire assembly was then placed in a 155° C. ovenfor 11/2 hours. After cooling, the plastic test sample was rinsed withmethyl ethyl ketone, dried and irradiated with ultraviolet light. Thesample turned from colorless to a light gray.

0.5 milliliters of methylene chloride was added to the original solutiondue to evaporation of the solvent and another piece of filter paperimmersed in the solution. The paper absorbed almost all of the solution.The paper was allowed to air dry and then placed on the same piece ofplastic test sample on the same side that had been previously treated. Apiece of untreated filter paper was placed on the other side of thesample and the sandwich placed between two plates of tempered glass. Theassembly was placed in a 155° C. oven for about 2 hours. After theassembly had cooled, the plastic sample was removed, rinsed with methylethyl ketone and irradiated with ultraviolet light. The sample turnedfrom a light yellow to gray.

EXAMPLE 5

A photochromic solution was prepared by combining 1.0 milliliters ofmethylene chloride, 0.096 grams of 5,7-dimethoxy-1',3',5'-trimethyl-3'-ethyl-6'-chlorospiro[2H-1,4-benzoxazine-2,2'-indoline] and 0.021 grams of 1,3,3-trimethylspiro(indolino)-2,3'[3H]pyrido[3,2-f][1,4]benzoxazine]. A piece of Balston No. 50filter paper as described in Example 4 was placed in the solution andthen removed and allowed to air dry for 13/4 hours. The dried filterpaper was placed on top of a small sample of undercured plastic preparedfrom diethylene glycol bis(allyl carbonate) and the assembly placedbetween two glass plates. The entire assembly was placed in a 150° C.oven for 2 hours. The assembly was allowed to cool to room temperature,the plastic test sample rinsed with methyl ethyl ketone and irradiatedwith ultraviolet light at 365 nanometers. The sample turned fromcolorless to blue/gray and faded through a gray stage.

EXAMPLE 6

The procedure of Example 5 was followed using 0.5 milliliters ofmethylene chloride, 0.059 grams of the spiro(indoline) benzoxazinecompound of Example 5 and 0.0092 grams of the spiro(benzindolino)naphthoxazine compound of Example 3. When irradiated with ultravioletlight, the sample turned a bluish gray color. A further sample wasprepared utilizing a photochromic solution prepared from 1.0 millilitersof methylene chloride, 0.134 grams of the spiro(indolino) benzoxazinecompound and 0.008 grams of the spiro(benzindolino) naphthoxazinecompound. Upon irradiation with ultraviolet light, the test samplechanged from a light yellow to gray.

EXAMPLE 7

The procedure of Example 5 was followed using a solution prepared from1.0 milliliters of methylene chloride, 0.095 grams of thespiro(indolino) benzoxazine compound of Example 5 and 0.0086 grams ofthe spiro(indolino) pyridobenzoxazine compound of Example 5. Uponirradiation with ultraviolet light, the sample changed from a lightyellow to a bluish gray color.

EXAMPLE 8

A 2 inch (5.1 centimeter) square of Whatman® 4 filter paper wassaturated with a 10 weight percent solution of a 8:1 (mole ratio)mixture of 5,7-dimethoxy-1',3',3',5',6' (and 4')pentamethylspiro[2H-1,4-benzoxazine-2,2'-indoline] and 1,3,3,5,6 (and4)-pentamethylspiro[indo -lino-2,3'[3H[ pyrido[3,2-f][1,4]benzoxazine intoluene. The filter paper was air dried until free of toluene.

The filter paper containing the photochromic compounds was placed on a 2inch (5.1 centimeter) square, 2.2 millimeters thick slightly undercuredplastic sample prepared from diethylene glycol bis(allyl carbonate). Thepaper covered plastic was placed between two aluminum plates (0.125inch×2.25 inch×2.25 inch [0.3175 centimeters×5.715 centimeters×5.715centimeters]) and the assembly heated in an oven at 150° C. for 90minutes. The assembly was cooled and the photochromic surface of thecooled plastic cleaned with acetone. The foregoing imbibition processwas repeated using a fresh sample of filter paper containing anidentical mixture of the aforedescribed photochromic compounds to treatthe photochromic surface of the cleaned plastic sample.

After another acetone cleaning, the photochromic plastic sample wastinted sequentially with A.0. Autumn and then Rodenstock Maron dyes(Brain Power, Inc.) by immersing it in an aqueous dispersed dye bath forless than 2 minutes at 83° C. The resulting yellow-brown plastic had aluminous transmission of 80 percent.

The photochromic tinted plastic sample was exposed to simulated solarradiation from a 1000 watt xenon lamp (UV intensity at 365nanometers=1.25 mW per square centimeter). The temperature of the samplewas maintained at 25° C. After activation, the sample was gray with aluminous transmission of 46 percent.

EXAMPLE 9

A 2 inch (5.1 centimeter) square of Whatman® 4 filter paper wassaturated with a 10 weight percent solution of a 8:1 (mole ratio)mixture of5,7-dimethoxy-3',3'-dimethyl-1'-n-propylspiro[2H-1,4-benzoxazine-2,2'-indoline]and 1-n-propyl-3,3-dimethyl-5-methoxyspiro[indolino-2,3'[3H] pyrido [3,2-f][1,4]benzoxazine]in toluene. The filter paperwas air dried until free of toluene.

The filter paper containing the photochromic compounds was placed on a 2inch (5.1 centimeter) square 2.2 millimeters thick slightly undercuredplastic sample prepared from diethylene glycol bis(allyl carbonate). Thefilter paper covered plastic sample was placed between two aluminumplates (0.125 inch×2.25 inch×2.25 inch [0.3175 centimeters×5.715centimeters×5.715 centimeters]) and the assembly heated in an oven at150° C. for 90 minutes. The assembly was cooled and the photochromicsurface of the cooled plastic cleaned with acetone. The foregoingimbibition process was repeated using a fresh sample of filter papercontaining an identical mixture of photochromic compounds to treat thephotochromic surface of the cleaned plastic sample.

After another acetone cleaning, the photochromic sample was tinted withA. 0. Cosma-Lite (Brain Power, Inc.) by immersing it in an aqueousdispersed dye bath for less than 2 minutes at 83° C. The resulting lightbrown plastic sample had a luminous transmission of 74 percent.

The photochromic tinted plastic sample was exposed to simulated solarradiation from a 1000 watt xenon lamp (UV intensity at 365nanometers=1.25 mW per square centimeter). The temperature of the samplewas maintained at 78° F.(25° C). After activation, the sample was graywith a luminous transmission of 42 percent. The chromaticity coordinatesafter activation were: x=0.276, y=0.306, as measured on a SpectrogardColor Spectrophotometer.

EXAMPLE 10

The procedure described in Example 9 was repeated except that the finaltinting operation was omitted. The unactivated sample was very slightlyyellow in color (luminous transmission= 89 percent). The sample wasexposed to solar radiation (UV intensity at 365 nanometers=0.94 mW persquare centimeter) for 30 minutes at 7.5° C. The activated sample wasblue-gray with a luminous transmission of 23 percent. After fading to aluminous transmission of 40 percent, the chromaticity coordinates weredetermined to be: x=0.267, y=0.280.

EXAMPLE 11

The general procedure of Example 9 was used to prepare a plastic sampleusing only 1-n-propyl-3,3-dimethyl-5-methoxyspiro[in-dolino- 2-3'[3H]pyrido [3,2-f][1,4]benzoxazine]. Only one imbibition procedure was usedand the plastic sample was not tinted Upon exposure to solar radiation,the very light yellow sample became bright blue. The chromaticitycoordinates determined at 40 percent luminous transmission were:x=0.216,y=0.253.

Although the present invention has been described with reference tospecific details of certain embodiments thereof, it is not intended thatsuch details should be regarded as limitations upon the scope of theinvention, except as and to the extent that they are included in theaccompanying claims.

We claim:
 1. A method for imparting photochromicity to an organic hostmaterial, which comprises placing in near proximity to or in contactwith the surface of the host material (a) a first organic photochromicsubstance selected from the group consisting of spiro(indolino)naphthoxazines, spiro(indolino) pyridobenzoxazines, spiro(benzindolino)pyridobenzoxazines and spiro(benzindolino) naphthoxazines, and having anactivated absorption maximum in the visible range of greater than 590nanometers in said host material and (b) a second organic photochromicspiro(indolino) benzoxazine substance having at least one activatedabsorption maximum in the visible range of between 400 nanometers andless than 590 nanometers in said host material, and incorporating bythermal transfer said first and second organic photochromic substancesinto said surface of the host material, said first and second organicphotochromic substances being present in said surface in photochromicamounts and in such a relative proportion that the spectralcharacteristics of the surface of the organic host material is a nearneutral color when the surface is exposed to solar radiation.
 2. Themethod of claim 1 wherein the mole ratio of the first organicphotochromic substance to the second organic photochromic substancevaries from about 1:0.5 to about 1:15.
 3. The method of claim 2 whereinthe first organic photochromic substance is represented by the followinggraphic formula, ##STR15## and the second organic photochromic substanceis represented by the following graphic formula, ##STR16## wherein: (a)R₁ is selected from the group consisting of C₁ -C₄ alkyl, phenyl,benzyl, 1-naphth-(C₁ -C₂)alkyl, carboxy(C₂ -C₄)alkyl, cyano(C₂-C₄)alkyl, C₁ -C₄)acyloxy(C₂ -C₄)alkyl, hydroxy(C₂ -C₄)alkyl and (C₂ H₄O)_(m) CH₃ wherein m is a number of from 1 to 3,(b) R₂ and R₃ are eachselected from the group consisting of C₁ -C₅ alkyl and phenyl, (c) Y isselected from carbon and nitrogen, (d) each R₄, when Y is carbon, isselected form the group consisting of C₁ -C₂ alkyl, C₁ -C₂ alkoxy,halogen, nitro, and C₁ -C₂ polyhaloalkyl, (e) each R₄, when Y isnitrogen, is selected from the group consisting of C₁ -C₂ alkyl, C₁ -C₂alkoxy and halogen, (f) each R₅ is selected from the group consisting ofC₁ -C₅ alkyl, halogen, C₁ -C₅ alkoxy, nitro, cyano, C₁ -C₄monohaloalkyl, C₁ -C₄ polyhaloalkyl, C₁ -C₈ alkoxycarbonyl, C₁ -C₄acyloxy, phenylene and substituted phenylene, said phenylenesubstituents ranging in number from 0 to 2 and being selected from thegroup consisting of halogen, C₁ -C₅ alkyl, C₁ -C₅ alkoxy, cyano, C₁ -C₈alkoxycarbonyl, C₁ -C₂ polyhaloalkyl, C₁ -C₄ monohaloalkyl, and mono- ordi(C₁ -C₄) aklylamino, (g) e is an integer of from 0 to 2, and d is aninteger of from 0 to 4; provided that when an R₅ substituent isphenylene or substituted phenylene, d is an integer of from 1 to 2 andwhen d is 2 the second substituent is other than a phenylene group, (h)each R₇ is a C₁ -C₂ alkyl, C₁ -C₂ alkoxy, halogen, nitro ortrihaloalkyl, (i) each R₈ is a C₁ -C₂ alkyl, halogen, C₁ -C₅ alkoxy orC₁ -C₂ trihaloalkyl, (j) g is an integer of from 1 to 2, and h is aninteger of from 0 to
 2. 4. The method of claim 3 wherein the organichost material is selected from the group consisting essentially ofhomopolymers and copolymers of diethylene glycol bis(allyl carbonate),polyacrylates, poly(alkylacrylates), homopolymers and copolymers ofpolyfunctional acrylate monomers, cellulose acetate, cellulosetriacetate, cellulose acetate propionate, cellulose acetate butyrate,poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride),poly(vinylidene chloride), polycarbonate, polyurethanes, poly(ethyleneterephthalate), polystyrene, copoly(styrene-methylmethacrylate),copoly(styrene-acrylonitrile), polyvinylbutyral, and homopolymers andcopolymers of diallylidene pentaerythritol.
 5. The method of claim 3wherein the organic host material is selected from homopolymers andcopolymers of diethylene glycol bis(allyl carbonate).
 6. The method ofclaim 5 wherein the organic host material is a lens.
 7. The method ofclaim 6 wherein the first and second organic photochromic substances aresimultaneously thermally transferred into a surface of the hostmaterial.
 8. The method of claim 6 wherein a mixture of the first andsecond organic photochromic substances are applied to a temporarysubstrate and simultaneously thermally transferred into a surface of thehost material.
 9. The method of claim 7 wherein the surface of the hostmaterial is treated at least twice with the photochromic substances. 10.The method of claim 7 wherein the organic host material is tinted with acompatible dye following thermal transfer of the photochromicsubstances.
 11. The method of claim 1 wherein the first organicphotochroic substance exhibits an activated absorption maximum in thevisible range of from greater than 590 nanometers to about 700nanometers.
 12. The method of claim 2 wherein the first organicphotochromic substance may be represented by the following graphicformula: ##STR17## wherein, (a) R₁ is selected from the group consistingof C₁ -C₄ alkyl, phenyl, benzyl, 1-naphth(C₁ -C₂)alkyl, carboxy(C₂-C₄)alkyl, cyano(C₂ -C₄)alkyl, C₁ -C₄ acyloxy(C₂ -C₄)alkyl, hydroxy(C₂-C₄)alkyl and (C₂ H₄ O)_(m) CH₃, wherein m is a number of from 1 to3,(b) R₂ and R₃ are each selected from the group consisting of C₁ -C₅alkyl and phenyl, (c) each R₄ is selected from the group consisting ofC₁ -C₅ alkyl, C₁ -C₅ alkoxy and halogen, and the letter e is an integerfor 0 to 1, (d) each R'₅ is selected from the group consisting of C₁ -C₅alkyl, halogen, C₁ -C₅ alkoxy, nitro, cyano, C₁ -C₄ monohaloalkyl, C₁-C₄ polyhaloalkyl, C₁ -C₈ alkoxycarbonyl and C₁ -C₄ acyloxy, and theletter d is an integer of from 0 to
 4. 13. The method of claim 12wherein the first organic photochromic substance is selected from thegroup consisting of (a)1,3,3-trimethylspiro[indolino-2,3'[3H]pyridol[3,2-f][1,4] benzoxazine],(b) 1,3,3,5,6(and4)-pentamethylspiro[indolino-2,3'[3H]-pyrido[3,2,-f][1,4]benzoxazine],and (c) 1-n-propy-3,3-dimethyl-5-methoxyspiro[indolino-2,3'[3H]pyrido[3,2-f][1,4]benzoxazine].14. The method of claim 2 wherein the first organic photochromicsubstance may be represented by the following graphic formula: ##STR18##wherein, (a) ring B is a substituted or unsubstituted benzene ring fusedat the e, f, or g face of the indolino segment of the substance,(b) R₉is selected from the group consisting of hydrogen, halogen, C₁ -C₅alkyl, C₁ -C₅ alkoxy, C₁ -C₄ monohaloalkyl, C₁ -C₂ polyhaloalkyl, cyanoand C₁ -C₈ alkoxycarbonyl, (c) R₆ is selected from the group consistingof halogen, C₁ -C₅ alkyl, C₁ -C₅ alkoxy, cyano, C₁ -C₈ alkoxycarbonyl,C₁ -C₄ monohaloalkyl, C₁ -C₂ polyhaloalkyl and mono- or di(C₁-C₄)alkylamino, (d) the letter c is an integer of from 0 to 2, and (e)R₁, R₂, R₃, R₄, Y and the letter e are the same as defined in claim 3.15. The method of claim 14 wherein the first organic photochromicsubstance is selected from the group consisting of:9'-methoxy-1,3,3-trimethylspiro[benz[g]indolino-2,3'[3H]naphth[2,1-b][1,4] oxazine], and9'-methoxy-1,3,3-trimethylspiro[benz[e]indolino 2,3'[3H]naphth[2,1-b][1,4]oxazine].
 16. The method of claim 3 wherein the secondorganic photochromic substance is selected from the group consistingof:(a) 5,7-dimethoxy-1',3'-dimethyl-3'-ethyl-4'(and 6')fluorospiro[2H-1,4-benzoxazine-2,2'-indoline], (b)5,7-dimethoxy-1',3',3'-trimethyl-4'(and 6')fluorospiro[2H-1,4-benzoxazine-2,2'-indoline], (c)5,7-dimethoxy-1',3',5'-trimethyl-3'-ethyl-6'-chlorospiro[2H-1,4-benzoxazine-2,2'-indoline],(d) 5,7-dimethoxy-1',3',3',5',6'(and 4') pentamethyl-spiro[2H-1,4-benzoxazine-2,2'-indoline], and (e)5,7-dimethoxy-3',3'-dimethyl-1'-n-propylspiro[2H-1,4-benzoxazine-2,2'-indoline].